CN115197184A - Luminescent auxiliary material and preparation method and application thereof - Google Patents

Luminescent auxiliary material and preparation method and application thereof Download PDF

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CN115197184A
CN115197184A CN202210803099.3A CN202210803099A CN115197184A CN 115197184 A CN115197184 A CN 115197184A CN 202210803099 A CN202210803099 A CN 202210803099A CN 115197184 A CN115197184 A CN 115197184A
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reactant
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auxiliary material
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汪康
贾宇
孙向南
徐佳楠
马晓宇
张雪
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention provides a luminescent auxiliary material and a preparation method and application thereof, wherein the structural general formula is shown in the specification, the luminescent auxiliary material provided by the invention takes dibenzofuran, dibenzothiophene, carbazole and dimethylfluorene as frameworks, and is connected with an arylamine group and an adamantyl group through a phenyl group with a bridged pi group, wherein the adamantine has high spatial symmetry and a rigid structure, and is introduced into a condensed ring unit, so that the thermal stability of the material can be effectively improved, and meanwhile, the introduction of an adamantane construction unit obviously improves the physical and chemical properties of the material, is beneficial to improving the performance of a device and prolonging the service life of the device. The triarylamine group enables the triarylamine group to have strong hole transmission capability, the triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules, prevent the molecules from moving on a plane, and simultaneously, the high hole transmission rate can reduce the driving voltage of the device, improve the efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device.

Description

Luminescent auxiliary material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a luminous auxiliary material and a preparation method and application thereof.
Background
Since 2000, organic electroluminescent devices (OLEDs) have attracted considerable attention, and have been widely used in the fields of displays, lighting, etc. due to their advantages of self-luminescence, high luminous efficiency, full-color display, low power consumption, low driving voltage, etc. due to their rapid development. Organic electroluminescence utilizes the photoelectric functional characteristics of an organic semiconductor material to directly convert electric energy into light energy, belongs to carrier injection type luminescence, forms excitons by recombination of holes injected from an anode and electrons injected from a cathode in a light emitting layer, and releases energy in the form of light energy. The OLED device is structurally divided into a single-layer device structure, a double-layer device structure, a three-layer device structure, a multi-layer device structure and the like, the three-layer device structure is the most widely used at present, namely the OLED device has a multi-functional-layer structure comprising an electron transport layer, a light emitting layer, a hole transport layer and the like, and the three functional layers respectively play roles to optimize the performance of the OLED device.
The Hole Transport Layer (HTL) is responsible for adjusting the injection speed and injection amount of holes, however, most of the current hole transport layer materials have thermal stress between the anode and the hole injection layer when the OLED is driven at high current, and the thermal stress significantly reduces the lifespan of the device; since the organic material used in the hole transport region has very high hole mobility, the hole-electron charge balance may be disrupted and the quantum efficiency (cd/a) may be reduced.
In order to solve the above problems, it is general to add a light-emitting auxiliary layer between the hole transport layer and the light-emitting layer (i.e., to provide the above-mentioned multiple hole transport layers) to improve the device lifetime and efficiency. The light-emitting auxiliary layer can increase the utilization rate of holes, thereby improving the light-emitting efficiency and the service life and reducing the driving voltage. But nowadays the luminescence auxiliary layer material is relatively small and faces the problem of having a less pronounced gain effect. The development of organic functional materials with higher performance is imminent.
Therefore, it is an urgent technical problem in the art to develop a light-emitting auxiliary material that can significantly improve the lifetime of a blue-ray device and improve the light-emitting efficiency, BI value, and driving voltage to some extent.
Disclosure of Invention
In view of the above, the present invention provides a luminescent auxiliary material, and a preparation method and an application thereof.
The luminescent auxiliary material provided by the invention can obviously prolong the service life of a blue light device, and simultaneously improves the luminous efficiency, the BI value and the driving voltage to a certain extent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a luminescent auxiliary material, the structural general formula of the luminescent auxiliary material is shown as formula I:
Figure BDA0003735074040000011
wherein the content of the first and second substances,
the ring B is selected from aryl with 6-20 carbon atoms;
x is selected from O and-NR 2 、-C(R 3 )(R 4 ) -or S;
R 1 selected from hydrogen, substituted or unsubstituted alkyl with 1 to 12 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, or substituted or unsubstituted 3 to 30-membered heteroaryl;
R 2 selected from substituted or unsubstituted aryl with 6 to 30 carbon atoms or substituted or unsubstituted 3 to 30-membered heteroaryl;
R 3 -R 4 each independently selected from substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, or substituted or unsubstituted 3 to 30-membered heteroaryl;
Ar 1 、Ar 2 each independently selected from a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, wherein the heteroatom is selected from N, O, S, si, P or Se; substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 20 carbon atoms, wherein the heteroatom is selected from N, O, S, si, P or Se; a substituted or unsubstituted condensed ring group having 10 to 30 carbon atoms, or a substituted or unsubstituted spiro ring group having 5 to 30 carbon atoms.
Further, the structural formula of the above-mentioned light-emitting auxiliary material is selected from any one of the following structural formulas:
Figure BDA0003735074040000021
further, the ring B is a phenyl group.
Further, the above R 1 Is any one of hydrogen, methyl, ethyl, tert-butyl, methylbenzene, methoxyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorene, benzofuran, benzothiophene and pyridyl;
r is as defined above 2 Is phenyl, naphthyl, biphenyl, phenanthryl, carbazoleAny one of fluorenyl, dimethyl fluorene, terphenyl, benzofuran, benzothiophene and pyridyl.
Further, the above R 3 -R 4 Each independently selected from methyl, ethyl, phenyl, methyl benzene, biphenyl or naphthyl.
Further, ar mentioned above 1 And Ar 2 Is connected with N at any connectable position, ar 1 、Ar 2 Each independently selected from the group consisting of:
Figure BDA0003735074040000031
further, the structural formula of the above-mentioned light-emitting auxiliary material is selected from any one of the following structural formulas:
Figure BDA0003735074040000041
in the present specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a silyl group; a boron group; C1-C6 alkyl; C3-C10 cycloalkyl; a C6-C18 aryl group; a heterocyclic group of C3 to C30, or a substituent in which two or more substituents among the above-shown substituents are bonded, or no substituent.
Further, the structural formula of the above-mentioned luminescence auxiliary material is selected from any one of the following structural formulas:
Figure BDA0003735074040000051
Figure BDA0003735074040000061
Figure BDA0003735074040000071
Figure BDA0003735074040000081
Figure BDA0003735074040000091
Figure BDA0003735074040000101
Figure BDA0003735074040000111
Figure BDA0003735074040000121
Figure BDA0003735074040000131
Figure BDA0003735074040000141
Figure BDA0003735074040000151
Figure BDA0003735074040000161
Figure BDA0003735074040000171
Figure BDA0003735074040000181
Figure BDA0003735074040000191
the invention also provides a preparation method of the luminescent auxiliary material, which comprises the following steps:
(1) Under the protection of nitrogen, adding a reactant A-I, a reactant B-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating, reacting, cooling to room temperature after the reaction is finished, performing suction filtration after solid precipitation is finished, washing with water to remove salt, leaching with ethanol, drying a filter cake, and recrystallizing in 1,4-dioxane to obtain a compound shown as an intermediate C-I;
(2) After adding the intermediate C-I and the reactant D-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 t-BuONa; after the addition, the reaction temperature was slowly raised, and the mixture was stirred; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; purifying the remaining substance by column chromatography with dichloromethane and petroleum ether as eluent to obtain compound intermediate E-I;
(3) After adding the intermediate E-I and the reactant F-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 t-BuONa; after the addition, the reaction temperature was slowly raised, and the mixture was stirred; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; with dichloromethane and stonePurifying the remaining substance by column chromatography using oleyl ether as eluent to obtain a luminescent auxiliary material represented by general formula I;
hal as described above 2 Is any one of chlorine, bromine or iodine;
the synthesis route of the luminescent auxiliary material shown in the general formula I is as follows:
Figure BDA0003735074040000201
further, in the step (1), the molar ratio of the reactant A-I, the reactant B-I, the tetrakis (triphenylphosphine) palladium and the potassium carbonate is 1 (1.1-1.2): (0.01-0.02): (2.0-2.3).
In step (1), the volume ratio of toluene, ethanol and water is (2-4): 1:1.
Further, in the step (1), the temperature is increased to 80-100 ℃ and the reaction lasts for 8-12h.
Further, in the step (2), the intermediate C-I and the reactant D-I, pd are obtained 2 (dba) 3 、P(t-Bu) 3 The molar ratio of t-BuONa is 1.0 (1.0-1.4) to 0.01 (0.02-0.04) to 2.0-2.4).
Further, in the step (2), the volume ratio of the dichloromethane to the petroleum ether is 1 (1-9).
Further, in the step (2), the reaction temperature is slowly raised to 105-115 ℃, and the mixture is stirred for 8-12h.
Further, in the step (3), the intermediate E-I and the reactant F-I, pd are obtained 2 (dba) 3 、P(t-Bu) 3 The molar ratio of t-BuONa is 1.0 (1.0-1.4) to 0.01 (0.02-0.04) to 2.0-2.4).
Further, in the step (3), the volume ratio of the dichloromethane to the petroleum ether is 1 (2-7).
Further, in the step (3), the reaction temperature is slowly raised to 105-115 ℃, and the mixture is stirred for 8-12h.
Further, the preparation method of the intermediate B-I comprises the following steps:
1) Under the protection of nitrogen, adding the reactant 1 into tetrahydrofuran, cooling, and slowly dropwise adding n-BuLi to obtain a reaction solution of an intermediate 2;
2) Under the protection of nitrogen, the reaction solution containing the intermediate 2, the reactant 3, and palladium acetate (Pd (OAc) 2 ) 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos), cesium carbonate is dissolved in tetrahydrofuran, the temperature is raised, the reaction is carried out, the reaction product is cooled to the room temperature, H is added 2 Separating liquid, removing the solvent from the organic layer by using a rotary evaporator, heating and dissolving the obtained solid by using toluene, passing the solid through a silica gel funnel while the solid is hot, removing the solvent from the obtained rotary evaporator by using methanol and dichloromethane as developing agents, and drying the obtained solid to obtain an intermediate 4;
3) Under the protection of nitrogen, dissolving the intermediate 4 in THF (tetrahydrofuran) for cooling, slowly dropwise adding n-BuLi, reacting, heating to room temperature, adding a reactant 5, namely triisopropyl borate into a mixed solvent, fully reacting overnight, adding hydrochloric acid, adjusting the pH value of the solution to 1-2, acidifying, separating liquid, combining organic phases, drying by using anhydrous magnesium sulfate, removing the solvent by using a rotary evaporator to obtain a solid organic matter, completely dissolving the solid organic matter by using dichloromethane, slowly dropwise adding the solid organic matter into a petroleum ether solution, uniformly stirring, precipitating a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using anhydrous ethanol and petroleum ether, and drying to obtain a reactant B-I;
hal above 1 Any one selected from chlorine, bromine and iodine;
the synthetic route of the intermediate B-I is as follows:
Figure BDA0003735074040000211
further, in the step 1), the molar ratio of the reactant 1 to the n-BuLi is 1.0 (1.1-1.5).
Further, in the step 1), the temperature is reduced to-78 ℃.
Further, in the step 2), the molar ratio of the intermediate 2, the reactant 3, the palladium acetate, the 2-cyclohexyl-2,4,6-triisopropylbiphenyl to the cesium carbonate is 1.0 (1-1.2), 0.01-0.05, (0.01-0.05) and 2.0-2.3.
Further, in the step 2), the volume ratio of the methanol to the dichloromethane is 1 (40-60).
Further, in the step 2), the temperature is increased to 40-70 ℃ for reaction for 2-8h.
Further, in the step 3), the molar ratio of the intermediate 4, the n-BuLi and the reactant 5 is 1.0 (1.1-1.5) to (1.1-1.4).
In the above terms of the present invention, the "slow temperature rise" is a temperature rise rate adjustment according to actual operation conditions, and contributes slowly to the completion of the reaction and the smooth progress of the reaction.
The invention also provides an application of the luminescent auxiliary material or the luminescent auxiliary material prepared by the method in preparation of organic electroluminescent devices.
Further, the organic electroluminescent device includes a first electrode, a second electrode provided to face the first electrode, and 1 or more organic layers between the first electrode and the second electrode, wherein at least 1 of the organic layers contains the light-emitting auxiliary material.
Further, the organic layer may further include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emission auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
Further, the organic layers may be composed of the same substance or different substances.
Further, the light-emitting auxiliary material is used for preparing an organic layer by a vacuum evaporation method or a solution coating method in the manufacture of an organic electroluminescent device.
Further, the solution coating method is any one of a spin coating method, a dip coating method, a blade coating method, an ink jet printing method, a screen printing method, a spray method, and a roll coating method.
Further, the organic electroluminescent device is of a top emission type, a bottom emission type, or a bidirectional emission type.
Further, the organic electroluminescent device is used for preparing an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
The invention has the beneficial effects that: according to the invention, dibenzofuran, dibenzothiophene, carbazole and dimethylfluorene are used as frameworks and are connected with an arylamine group and an adamantyl group through a phenyl group with a bridged pi group, wherein the adamantine has high spatial symmetry and a rigid structure and is introduced into a condensed ring unit, so that the thermal stability of the material can be effectively improved, and meanwhile, the introduction of an adamantane building unit obviously improves the physical and chemical properties of the material, thereby being beneficial to improving the performance of a device and prolonging the service life of the device.
The triarylamine group enables the triarylamine group to have strong hole transmission capability, the triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules, prevent the molecules from moving on a plane, and simultaneously, the high hole transmission rate can reduce the driving voltage of the device, improve the efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 22;
FIG. 2 shows the NMR spectrum of Compound 41.
Detailed Description
The following examples are intended to illustrate the present invention, but are not intended to limit the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The synthetic route of the reactant B-1 is as follows:
Figure BDA0003735074040000221
CAS: reaction b-1:397243-08-2
CAS: reactant b-3:13101-40-1
Step 1:
under the protection of nitrogen, adding a reactant b-1 (400 mmol) into tetrahydrofuran, cooling to-78 ℃, and slowly dropwise adding n-BuLi (440 mmol) to obtain a reaction solution of an intermediate b-2;
step 2:
under the protection of nitrogen, the nitrogen-containing organic solvent contains an intermediateReaction solution (400 mmol) of b-2, reactant b-3 (480 mmol), and palladium acetate (Pd (OAc) 2 ) (4 mmol), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (8 mmol), cesium carbonate (840 mmol) were dissolved in tetrahydrofuran, warmed to 50 ℃ for 4H, cooled to room temperature, and H was added 2 O, separating the liquid, removing the solvent from the organic layer by a rotary evaporator, dissolving the obtained solid by heating with toluene, passing through a silica gel funnel while it is hot, and removing the solvent with methanol: the volume ratio of methylene chloride was 1 (40-60) as a developing solvent, the obtained rotary evaporator was removed of the solvent, and the obtained solid was dried to obtain an intermediate b-4 (45.62g, mw 325.91, yield: 35%);
and step 3:
under the protection of nitrogen, dissolving the intermediate b-4 (140 mmol) in 1400ml THF, cooling to-78 deg.C, slowly adding n-BuLi (154 mmol) dropwise, reacting for 2h, heating to room temperature, adding the reactant b-5 (154 mmol) (triisopropyl borate) in a mixed solvent, fully reacting overnight, adding hydrochloric acid, and adjusting the pH value of the solution to 1-2 for acidification. The organic phases were separated, combined, dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic material. The used dichloromethane completely dissolves the solid organic matter, then slowly dropwise adds the dissolved organic matter into the petroleum ether solution, evenly stirs the solution, precipitates, and obtains a solid by suction filtration, and the solid is sequentially leached by absolute ethyl alcohol and petroleum ether and dried, thus obtaining a reactant B-1 (34.20g, mw 290.87, yield: 84%).
Example 1: synthesis of Compound 1
Figure BDA0003735074040000231
Step 1:
under the protection of nitrogen, adding a reactant A-1 (100 mmol), a reactant B-1 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) into a mixed solvent of toluene (4 ml), ethanol (200 ml) and water (200 ml), heating to 95 ℃, reacting for 8h, cooling to room temperature after the reaction is finished, performing suction filtration after solid is separated out, washing with water to remove salt, rinsing with ethanol, drying a filter cake, and putting the filter cake into 1,4-dioxane for recrystallization to obtain a compound (23.13 g, 56% yield and Mw: 413.12) shown as an intermediate C-1.
Step 2:
after adding intermediate C-1 (40 mmol) and reactant D-1 (46 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.4mmol)、P(t-Bu) 3 (0.8 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 8h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of 1: the remaining material was purified by column chromatography using dichloromethane and petroleum ether of (1-9) as an eluent to obtain compound intermediate E-1 (18.36 g, yield: 82%, mw: 559.86).
And step 3:
after adding intermediate E-1 (30 mmol) and reactant F-1 (36 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (0.6 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 105 ℃ and the mixture was stirred for 12h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of 1: the remaining material was purified by column chromatography using dichloromethane and petroleum ether of (2-7) as an eluent to obtain compound 1 (18.58 g, yield: 87%, mw: 712.08).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Mass spectrometry test: theoretical value is 711.91; the test value was 712.08.
Elemental analysis:
theoretical value: c,87.73; h,5.81; n,1.97; o,4.49
Test values are: c,87.62; h,5.92; n,2.05; o,4.58
Example 2: synthesis of Compound 22
Figure BDA0003735074040000241
Step 1:
the reaction was identical to that of intermediate C-1 of example 1, giving intermediate C-22;
step 2:
after adding intermediate C-22 (42 mmol) and reactant D-22 (54.6 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.42mmol)、P(t-Bu) 3 (1.05 mmol), t-BuONa (88.2 mmol); after the addition, the reaction temperature was slowly raised to 105 ℃ and the mixture was stirred for 12h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: (1-9) using dichloromethane and petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-22 (21.34 g, yield: 86.7%, mw: 586.02);
and step 3:
after adding intermediate E-22 (30 mmol) and reactant F-22 (39 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (63 mmol); after the addition, the reaction temperature was slowly raised to 115 ℃ and the mixture was stirred for 9h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1:(2-7) dichloromethane, petroleum ether as eluent, and column chromatography to obtain compound 22 (19.38 g, yield: 85.9%, mw: 752.23).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Mass spectrometry test: theoretical value 751.97; the test value was 752.23.
Elemental analysis:
theoretical value: c,87.85; h,6.03; n,1.86; o,4.26
Test values are: c,87.59; h,6.24; n,1.92; o,4.38
Hydrogen nuclear magnetic resonance spectroscopy: as shown in figure 1.
Example 3: synthesis of Compound 41
Figure BDA0003735074040000251
Step 1:
the reaction was identical to that of intermediate C-1 of example 1 to give intermediate C-41;
step 2:
after adding intermediate C-41 (42 mmol) and reactant D-41 (54.6 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.42mmol)、P(t-Bu) 3 (1.05 mmol), t-BuONa (88.2 mmol); after the addition, the reaction temperature was slowly raised to 105 ℃ and the mixture was stirred for 12h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: (1-9) using dichloromethane and petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-41 (21.2 g, yield: 84.7%, mw: 595.97);
and step 3:
after adding intermediate E-41 (30 mmol) and reactant F-41 (39 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (63 mmol); after the addition, the reaction temperature was slowly raised to 115 ℃ and the mixture was stirred for 9h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: the remaining material was purified by column chromatography using dichloromethane and petroleum ether of (2-7) as an eluent to obtain compound 41 (18.4 g, yield: 82%, mw: 748.34).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Mass spectrometry test: theoretical value is 747.98; the test value was 748.34.
Elemental analysis:
theoretical value: c,89.92; h,6.06; n,1.87; o,2.14
Test values are: c,89.61; h,6.28; n,1.95; o,2.28
Hydrogen nuclear magnetic resonance spectroscopy: as shown in fig. 2.
Example 4: synthesis of Compound 52
Figure BDA0003735074040000261
Step 1:
the reaction was identical to that of intermediate C-1 of example 1, giving intermediate C-52;
and 2, step:
after adding intermediate C-52 (30 mmol) and reactant D-52 (36 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mol)、P(t-Bu) 3 (0.6 mmol), t-BuONa (66 mmol); after the addition, the reaction temperature was slowedThe temperature was raised to 105 ℃ and the mixture was stirred for 12h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: (1-9) using dichloromethane and petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-52 (15.20 g, yield: 85%, mw: 595.94);
and step 3:
after adding intermediate E-52 (20 mmol) and reactant F-52 (26 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.2mmol)、P(t-Bu) 3 (0.8 mmol), t-BuONa (44 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 10h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: the remaining material was purified by column chromatography using dichloromethane and petroleum ether of (2-7) as an eluent to obtain compound 52 (13.55 g, yield: 88.9%, mw: 762.25).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Mass spectrum testing: theoretical value is 761.97; the test value was 762.25.
Elemental analysis:
theoretical values are as follows: c,88.27; h,5.69; n,1.84; o,4.20
Test values are: c,88.06; h,5.83; n,1.91; o,4.31
Example 5: synthesis of Compound 188
The synthetic route for reactant B-188 is as follows:
Figure BDA0003735074040000271
CAS: reactant b-8:148836-41-3
Step 1:
under the protection of nitrogen, adding a reactant b-6 (400 mmol) into tetrahydrofuran, cooling to-78 ℃, and slowly dropwise adding n-BuLi (440 mmol) to obtain a reaction solution of an intermediate b-7;
step 2:
under the protection of nitrogen, a reaction solution (400 mmol) containing intermediate b-7, reactant b-8 (480 mmol), and palladium acetate (Pd (OAc) 2 ) (4 mmol), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (8 mmol), cesium carbonate (840 mmol) were dissolved in tetrahydrofuran, warmed to 50 ℃ for 4H, cooled to room temperature, and H was added 2 O, separation, removal of solvent from the organic layer using a rotary evaporator, heating and dissolving the resulting solid with toluene, passing through a silica gel funnel while hot, eluting with methanol: the volume ratio of methylene chloride was 1 (40-60) as a developing solvent, the solvent was removed from the obtained rotary evaporator, and the obtained solid was dried to obtain intermediate b-9 (49.54g, mw 325.93, yield: 38%);
and step 3:
under the protection of nitrogen, dissolving the intermediate b-9 (140 mmol) in 1400ml of THF, cooling to-78 ℃, slowly adding n-BuLi (154 mmol) dropwise, reacting for 2h, raising to room temperature, adding the reactant b-10 (154 mmol) (triisopropyl borate) in a mixed solvent, fully reacting overnight, adding hydrochloric acid, and adjusting the pH value of the solution to be between 1 and 2 for acidification. The organic phases were separated, combined, dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic material. The used dichloromethane completely dissolves the solid organic matter, then slowly dropwise adds the solid organic matter into the petroleum ether solution, evenly stirs, precipitates and separates out, and obtains solid by suction filtration, and then the solid is sequentially leached by absolute ethyl alcohol and petroleum ether and dried, and a reactant B-188 (32.99g, mw 290.89, yield: 81%) is obtained.
Figure BDA0003735074040000281
Step 1:
under the protection of nitrogen, adding a reactant A-188 (100 mmol), a reactant B-188 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) into a mixed solvent of toluene (4 ml), ethanol (200 ml) and water (200 ml), heating to 95 ℃, reacting for 8 hours, cooling to room temperature after the reaction is finished, performing suction filtration after solid is separated out, washing with water to remove salt, rinsing with ethanol, drying a filter cake, and putting the filter cake into 1,4-dioxane for recrystallization to obtain a compound (24.90 g, 51% yield and Mw: 488.25) shown as an intermediate C-188;
step 2:
after adding intermediate C-188 (40 mmol) and reactant D-188 (46 mmol) in toluene in a reaction vessel, pd is added under the protection of nitrogen 2 (dba) 3 (0.4mmol)、P(t-Bu) 3 (1.12 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 8h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of 1: (1-9) using dichloromethane and petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-188 (21.61 g, yield 87%, mw: 621.03);
and 3, step 3:
after adding intermediate E-188 (30 mmol) and reactant F-188 (34.5 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (0.84 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 115 ℃ and the mixture was stirred for 8.5h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator(ii) a The volume ratio of the components is 1: ( 1-9) with petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound 188 (20.26 g, yield: 85.8%, mw:787.33 )
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Mass spectrometry test: theoretical value 787.02; the test value was 787.33.
Elemental analysis:
theoretical value: c,88.52; h,5.89; n,3.56; o,2.03
Test values are: c,88.28; h,6.10; n,3.61; o,2.10
Example 6: synthesis of Compound 268
Figure BDA0003735074040000291
Step 1:
under the protection of nitrogen, adding a reactant A-268 (100 mmol), a reactant B-268 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) into a mixed solvent of toluene (4 ml), ethanol (200 ml) and water (200 ml), heating to 95 ℃, reacting for 8 hours, cooling to room temperature after the reaction is finished, performing suction filtration after solid is separated out, washing with water to remove salt, rinsing with ethanol, drying a filter cake, and putting the filter cake into 1,4-dioxane for recrystallization to obtain a compound (24.16 g, 55% yield and Mw: 439.26) shown as an intermediate C-268;
step 2:
after adding intermediate C-268 (42 mmol) and reactant D-268 (46.2 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.42mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (84 mmol); after the addition, the reaction temperature was slowly raised to 105 ℃ and the mixture was stirred for 12h; filtering with diatomaceous earth, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting with ethyl acetateAn aqueous phase; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: (1-9) using dichloromethane, petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-268 (21.34 g, yield: 83%, mw: 612.05);
and step 3:
after adding intermediate E-268 (30 mmol) and reactant F-268 (33 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (0.9 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 10h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of 1: the remaining material was purified by column chromatography using dichloromethane and petroleum ether of (2-7) as an eluent to obtain compound 268 (20.20 g, yield: 86.5%, mw: 778.41).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Mass spectrometry test: theoretical value is 778.05; the test value was 778.41.
Elemental analysis:
theoretical value: c,89.54; h,6.61; n,1.8; o,2.06
Test values are: c,89.23; h,6.84; n,1.84; o,2.22
Example 7: synthesis of Compound 274
Figure BDA0003735074040000301
Step 1:
under the protection of nitrogen, adding a reactant A-274 (100 mmol), a reactant B-274 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) into a mixed solvent of toluene (4 ml), ethanol (200 ml) and water (200 ml), heating to 95 ℃, reacting for 8 hours, cooling to room temperature after the reaction is finished, performing suction filtration after solid is separated out, washing with water to remove salt, rinsing with ethanol, drying a filter cake, and putting the filter cake into 1,4-dioxane for recrystallization to obtain a compound (22.32 g, 52% yield and 429.22) shown as an intermediate C-274;
step 2:
after adding intermediate C-274 (40 mmol) and reactant D-274 (46 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.4mmol)、P(t-Bu) 3 (1.12 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 8h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: (1-9) using dichloromethane, petroleum ether as an eluent, and purifying the remaining substance by column chromatography to obtain compound intermediate E-274 (28.68 g, yield: 83%, mw: 575.98);
and step 3:
after adding intermediate E-274 (30 mmol) and reactant F-274 (33 mmol) in toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.3mmol)、P(t-Bu) 3 (0.9 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 110 ℃ and the mixture was stirred for 10h; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio of the components is 1: the remaining material was purified by column chromatography using methylene chloride of (2-7) and petroleum ether as an eluent to obtain compound 274 (28.18 g, yield: 86%, mw: 728.16).
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Mass spectrum testing: theoretical value is 727.97; the test value was 728.16.
Elemental analysis:
theoretical value: c,85.80; h,5.68; n,1.92; o,2.20; s,4.40
Test values are: c,85.45; h,5.87; n,1.99; o,2.31; s,4.46
Examples 8 to 70
The following compounds were prepared according to the synthetic methods of examples 1-7, and the formula and mass spectra are shown in Table 1:
TABLE 1 molecular formula, mass Spectrometry of the Compounds of examples 8-70
Figure BDA0003735074040000311
Figure BDA0003735074040000321
In addition, since other compounds of the present invention can be obtained by the synthesis methods according to the above-mentioned examples, they are not illustrated here.
Application example 1 preparation of organic electroluminescent device:
a. an ITO anode: cleaning an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning for 2 times by using distilled water, ultrasonically cleaning for 10min, transferring to a spin dryer for spin-drying after the cleaning is finished, finally baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after the baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003735074040000322
The hole injection layer materials HT and P-dopant are vacuum evaporated, and the chemical formulas are shown as follows. The evaporation rate ratio of HT to P-dopant is 98:2, the thickness is 10nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003735074040000323
The evaporation rate of (3), and evaporating 120nm HT as a hole transport layer on the hole injection layer in vacuum;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003735074040000324
Vacuum evaporation of 10nm of the compound 1 provided in the above example as a light-emitting auxiliary layer on top of the hole transport layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003735074040000332
The chemical formulas of Host and Dopant (span) are shown below, and the Host material (Host) and Dopant (span) are vacuum-evaporated to a thickness of 25nm as the light-emitting layer. Wherein the evaporation rate ratio of Host to Dopant is 97:3.
f. HB (hole blocking layer): to be provided with
Figure BDA0003735074040000333
The hole-blocking layer having a thickness of 5.0nm was vacuum-deposited at the deposition rate of (2). The chemical formula is shown as follows.
g. ETL (electron transport layer): to be provided with
Figure BDA0003735074040000334
The chemical formula of ET is shown below, and ET and Liq with the thickness of 35nm are vacuum-evaporated to form the electron transport layer. Wherein the evaporation rate ratio of ET to Liq is 50:50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003735074040000335
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003735074040000336
The evaporation rate ratio of (1) is that the evaporation rate ratio of magnesium to silver is 18nm, and is 1:9, so that the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003735074040000337
CPL was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer.
k. And packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The device structure is as follows:
ITO/Ag/ITO/HT P-dock (10nm, 2%)/HT (120 nm)/Compound 1 (10 nm)/Host: dock (25nm, 3%)/HB (5 nm)/ET: liq (35nm, 50%)/Yb (1 nm)/Mg: ag (18nm, 1).
Figure BDA0003735074040000331
[ application examples 2 to 70]
The organic electroluminescent devices of application examples 2 to 70 were prepared according to the above-described method for preparing an organic electroluminescent device, except that the compound 1 in application example 1 was replaced with the corresponding compound, respectively, to form a light-emitting auxiliary layer.
Comparative example 1
The organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in application example 1 was replaced with comparative compound 1.
Comparative example 2
An organic electroluminescent device was produced according to the above-described method for producing an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 2.
Comparative example 3
The organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in application example 1 was replaced with comparative compound 3.
Comparative example 4
The organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in application example 1 was replaced with comparative compound 4.
Comparative example 5
An organic electroluminescent device was produced according to the above-described production method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 5.
Comparative example 6
An organic electroluminescent device was produced according to the above-described production method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 6.
Comparative example 7
An organic electroluminescent device was produced according to the above-described production method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 7.
Comparative example 8
An organic electroluminescent device was produced according to the above-described production method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 8.
Comparative example 9
An organic electroluminescent device was produced according to the above-described production method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in application example 1 was replaced with comparative compound 9.
The structural formulas of comparative compounds 1-9 are as follows:
Figure BDA0003735074040000351
the organic electroluminescent devices obtained in the above device application examples 1 to 70 and the device comparative examples 1 to 9 were characterized at a luminance of 1000 (nits) for driving voltage, luminous efficiency, BI value and lifetime, and the test results are as follows in table 2:
TABLE 2 test results of luminescence characteristics (luminance: 1000 nits)
Figure BDA0003735074040000352
Figure BDA0003735074040000361
Figure BDA0003735074040000371
The invention uses dibenzofuran, dibenzothiophene, carbazole and dimethylfluorene as frameworks to be connected with an arylamine group and an adamantyl group through a phenyl group with a bridged pi group, wherein the adamantine has high spatial symmetry and a rigid structure and is introduced into a condensed ring unit, the thermal stability of the material can be effectively improved, the introduction of the adamantine building unit obviously improves the physical and chemical properties of the material, and the organic electroluminescent compound with excellent performance for a blue light luminescence auxiliary layer is obtained,
as can be seen from the above table, the performance of the luminescent-assist material devices used in comparative examples 1 to 9 and application examples 1 to 70 is significantly improved in lifetime. The luminous efficiency, the BI value and the driving voltage are also improved to a certain extent.
From experimental data, the main difference of compound 35 compared with comparative examples 2 and 3 is that the service life of the blue light device is prolonged by about 60h and is improved by nearly 40% by using adamantane. Compared with the comparative compound, the other compounds of the invention with adamantane generally improve the service life by about 20-40 percent, and have obviously improved the blue light service life.
In the field, the problem of short service life of the blue light device is one of the problems which are urgently needed to be solved by the technical personnel in the field, and the adamantane in the invention can obviously improve the structural stability of the compound, obviously improve the service life of the blue light device and is beneficial to the application in practical production.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A luminescent auxiliary material is characterized in that the structural general formula of the luminescent auxiliary material is shown as formula I:
Figure FDA0003735074030000011
wherein, the first and the second end of the pipe are connected with each other,
the ring B is selected from aryl with 6-20 carbon atoms;
x is selected from O and-NR 2 、-C(R 3 )(R 4 ) -or S;
R 1 selected from hydrogen, substituted or unsubstituted alkyl with 1 to 12 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, or substituted or unsubstituted 3 to 30-membered heteroaryl;
R 2 selected from substituted or unsubstituted aryl with 6 to 30 carbon atoms or substituted or unsubstituted 3 to 30-membered heteroaryl;
R 3 -R 4 each independently selected from the number of substituted or unsubstituted carbon atomsIs an alkyl group of 1 to 20, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted 3 to 30-membered heteroaryl group;
Ar 1 -Ar 2 each independently selected from substituted or unsubstituted cycloalkyl with 3-20 carbon atoms and substituted or unsubstituted heterocycloalkyl with 3-30 carbon atoms, wherein the heteroatom is selected from N, O, S, si, P or Se; substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 20 carbon atoms, wherein the heteroatom is selected from N, O, S, si, P or Se; a substituted or unsubstituted condensed ring group having 10 to 30 carbon atoms, or a substituted or unsubstituted spiro ring group having 5 to 30 carbon atoms.
2. A luminescent auxiliary material as claimed in claim 1, wherein the structural formula of the luminescent auxiliary material is selected from any one of the following structural formulas:
Figure FDA0003735074030000012
3. a luminescent support material as claimed in claim 1 or 2, wherein the ring B is a phenyl group.
4. A luminescent support material as claimed in claim 1 or 2, wherein R is a group of atoms 1 Is any one of hydrogen, methyl, ethyl, tert-butyl, methylbenzene, methoxy, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorene, benzofuran, benzothiophene or pyridyl;
said R is 2 Is any one of phenyl, naphthyl, biphenyl, phenanthryl, carbazolyl, fluorenyl, dimethyl fluorene, terphenyl, benzofuran, benzothiophene or pyridyl.
5. A luminescent support material as claimed in claim 1 or 2, wherein R is a group of atoms 3 -R 4 Each independently selected from methyl, ethyl, phenyl, methyl benzene, biphenyl or naphthyl.
6. A luminescent support material as claimed in claim 1 or 2, wherein Ar is present in a mixture of two or more of said materials 1 And Ar 2 Is connected with N at any connectable position, ar 1 、Ar 2 Each independently selected from the group consisting of:
Figure FDA0003735074030000021
7. a luminescent auxiliary material as claimed in claim 1 or 2, wherein the structural formula of the luminescent auxiliary material is selected from any one of the following structural formulas:
Figure FDA0003735074030000031
8. a method for preparing a luminescent support material as claimed in any one of claims 1 to 7, comprising the steps of:
(1) Under the protection of nitrogen, adding a reactant A-I, a reactant B-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating, reacting, cooling to room temperature after the reaction is finished, performing suction filtration after solid precipitation is finished, washing with water to remove salt, leaching with ethanol, drying a filter cake, and recrystallizing in 1,4-dioxane to obtain a compound shown as an intermediate C-I;
(2) After adding the intermediate C-I and the reactant D-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 t-BuONa; after the addition, the reaction temperature was slowly raised, and the mixture was stirred; filtering with diatomaceous earth, removing salt and catalyst, cooling the filtrate to room temperature, and adding distilled water to the filtrateWashing, separating, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; purifying the remaining substance by column chromatography with dichloromethane and petroleum ether as eluent to obtain compound intermediate E-I;
(3) After adding the intermediate E-I and the reactant F-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 t-BuONa; after the addition, the reaction temperature was slowly raised and the mixture was stirred; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; purifying the residual substance by column chromatography with dichloromethane and petroleum ether as eluent to obtain the luminescent auxiliary material shown in formula I;
said Hal 2 Is any one of chlorine, bromine or iodine;
the synthesis route of the luminescent auxiliary material shown in the general formula I is as follows:
Figure FDA0003735074030000041
9. the method for preparing a luminescence auxiliary material according to claim 8, wherein the method for preparing the intermediate B-I comprises the following steps:
1) Under the protection of nitrogen, adding the reactant 1 into tetrahydrofuran, cooling, and slowly dropwise adding n-BuLi to obtain a reaction solution of an intermediate 2;
2) Under the protection of nitrogen, the reaction solution containing the intermediate 2, the reactant 3, and palladium acetate (Pd (OAc) 2 ) 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos), cesium carbonate is dissolved in tetrahydrofuran, heated, reacted, cooled to room temperature, and H is added 2 O, separating liquid, and using a rotary evaporator for organic layerRemoving the solvent, heating and dissolving the obtained solid with toluene, passing through a silica gel funnel while the solid is hot, removing the solvent by using a rotary evaporator with methanol and dichloromethane as developing agents, and drying the obtained solid to obtain an intermediate 4;
3) Under the protection of nitrogen, dissolving the intermediate 4 in THF (tetrahydrofuran) for cooling, slowly dropwise adding n-BuLi, reacting, heating to room temperature, adding a reactant 5, namely triisopropyl borate into a mixed solvent, fully reacting overnight, adding hydrochloric acid, adjusting the pH value of the solution to 1-2, acidifying, separating liquid, combining organic phases, drying by using anhydrous magnesium sulfate, removing the solvent by using a rotary evaporator to obtain a solid organic matter, completely dissolving the solid organic matter by using dichloromethane, slowly dropwise adding the solid organic matter into a petroleum ether solution, uniformly stirring, precipitating a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using anhydrous ethanol and petroleum ether, and drying to obtain a reactant B-I;
said Hal 1 Is any one of chlorine, bromine or iodine;
the synthetic route of the intermediate B-I is as follows:
Figure FDA0003735074030000051
10. use of a luminescent support material according to any one of claims 1 to 7 or prepared by a process according to claim 8 or 9 for the preparation of an organic electroluminescent device.
CN202210803099.3A 2022-07-07 2022-07-07 Luminescent auxiliary material and preparation method and application thereof Pending CN115197184A (en)

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